CN101796227B - Process for growing single-crystal silicon carbide - Google Patents
Process for growing single-crystal silicon carbide Download PDFInfo
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- CN101796227B CN101796227B CN2008800253811A CN200880025381A CN101796227B CN 101796227 B CN101796227 B CN 101796227B CN 2008800253811 A CN2008800253811 A CN 2008800253811A CN 200880025381 A CN200880025381 A CN 200880025381A CN 101796227 B CN101796227 B CN 101796227B
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- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 238000000034 method Methods 0.000 title claims abstract description 71
- 229910021421 monocrystalline silicon Inorganic materials 0.000 title claims abstract description 44
- 239000013078 crystal Substances 0.000 claims abstract description 83
- 230000012010 growth Effects 0.000 claims abstract description 81
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000000758 substrate Substances 0.000 claims abstract description 30
- 239000010439 graphite Substances 0.000 claims abstract description 29
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 241000209456 Plumbago Species 0.000 claims description 22
- 239000002994 raw material Substances 0.000 claims description 18
- 229910052710 silicon Inorganic materials 0.000 claims description 17
- 229910052804 chromium Inorganic materials 0.000 claims description 9
- 229910045601 alloy Inorganic materials 0.000 claims description 8
- 239000000956 alloy Substances 0.000 claims description 8
- 229910010271 silicon carbide Inorganic materials 0.000 abstract description 43
- 229910002804 graphite Inorganic materials 0.000 abstract description 7
- 229910052759 nickel Inorganic materials 0.000 abstract description 3
- 229910052799 carbon Inorganic materials 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 229910052719 titanium Inorganic materials 0.000 description 7
- 230000007547 defect Effects 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 230000005855 radiation Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000005229 chemical vapour deposition Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- 239000012808 vapor phase Substances 0.000 description 3
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000009434 installation Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 230000000877 morphologic effect Effects 0.000 description 2
- 229910018106 Ni—C Inorganic materials 0.000 description 1
- 240000001439 Opuntia Species 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B9/00—Single-crystal growth from melt solutions using molten solvents
- C30B9/04—Single-crystal growth from melt solutions using molten solvents by cooling of the solution
- C30B9/08—Single-crystal growth from melt solutions using molten solvents by cooling of the solution using other solvents
- C30B9/10—Metal solvents
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B19/00—Liquid-phase epitaxial-layer growth
- C30B19/02—Liquid-phase epitaxial-layer growth using molten solvents, e.g. flux
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/36—Carbides
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B9/00—Single-crystal growth from melt solutions using molten solvents
- C30B9/04—Single-crystal growth from melt solutions using molten solvents by cooling of the solution
- C30B9/06—Single-crystal growth from melt solutions using molten solvents by cooling of the solution using as solvent a component of the crystal composition
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
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- Inorganic Chemistry (AREA)
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Abstract
A process of growing single-crystal silicon carbide on a single -crystal substrate by bringing a silicon carbide crystal into contact with Si melt heated in a graphite crucible, characterized in that single-crystal silicon carbide is precipitated and grown from an Si-Cr-X-C melt (wherein X is at least one element of Ni and Co) formed by adding Cr and X to the Si melt in such amounts that the contents of Cr and X in the whole composition fall within the range of 30 to 70at% and the range of 1 to 25at% respectively. The invention can realize improvement in the surface morphology of a crystal growth layer in the solution method.
Description
Technical field
The present invention relates to adopt the novel silicon carbide monocrystal growth method of solution method; More particularly; The growth method that relates to the single-crystal silicon carbide that adopts the solution method of having used novel fused solution (being also referred to as solution sometimes); This growth method has realized the raising of the form (morphology) of crystal growing surface, and the speed of growth is bigger.
Background technology
Silit (SiC) monocrystalline is at calorifics, chemically highly stable; Physical strength is also excellent, also ability raying line, and compare with Si have high breakdown voltage, the rerum natura of the excellence of high thermal conductivity etc.; Through adding impurity; Also carry out the electronically controlled of p, n conduction type easily, and possess and have wide energy gap (monocrystal SiC for the 6H type is about 3.0eV, is about 3.3eV for the monocrystal SiC of 4H type) this characteristic.Therefore can realize the irrealizable high temperature of existing semiconductor material, high frequency, the proof voltage and environment resistant of silicon (Si), gallium arsenic (GaAs) etc.,, its expectation improved as follow-on semiconductor material.
In the past, as the growth method of single-crystal silicon carbide, the known vapor phase process of representational method, Acheson's (Acheson) method and solution method.
Among subliming method and chemical Vapor deposition process (CVD) as the typical example of vapor phase process; Subliming method produces the various also easier crystallization of defective except crystal; The CVD method is because raw material supplying is restricted to gas, and the crystal that therefore generates is a film, is difficult to make bulk-shaped monocrystal.
In addition, in Acheson's method, owing to use silica and coke in electric furnace, to heat, therefore owing to impurities in raw materials etc. and can not high purityization as raw material.
In addition, solution method be in plumbago crucible with siliceous alloy melting, to this fused solution, be arranged at the crystal seed (seed crystal of low-temp. portion from plumbago crucible fusing carbon; Seed crystal) separates out and the method for grow silicon carbide crystals layer through solution on the substrate.Though and the speed of growth of known solution method is low, be suitable as the method that obtains bulk-shaped monocrystal.
Therefore, carried out the investigation that the speed of growth of the silicon carbide monocrystal growth method that the solution method of the problems referred to above that do not have vapor phase process, Acheson's method carries out is adopted in various raising recently.
In addition; The spy opens the method for manufacture that the 2000-264790 communique has been put down in writing a kind of single-crystal silicon carbide; Wherein, The raw materials melt that will contain at least a element, Si and C among the transition metal is processed fused solution, the silicon carbide seed crystal that makes monocrystalline with fused solution is cooled to the fused solution state that temperature is lower than the liquidus temperature of fused solution when fused solution contacts, make single-crystal silicon carbide separate out growth.And; The transition metal of giving an example out particularly is Fe, Co, Ni (above in VIII family), Ti, Zr, Hf (above in IVb family), V, Nb, Ta (above in Vb family), Cr, Mo and W (above in VIb family), is the situation of Mo, Cr, Co but concrete disclosed composition is a transition metal., unexposed about the quality of the monocrystalline of separating out to assay method and affirmation means, to the not identification of macroscopic defects of crystal growing surface.
The spy opens the method for manufacture that the 2004-2173 communique has been put down in writing a kind of single-crystal silicon carbide, wherein, at the atomic ratio that contains Si, C and M (side of M:Mn or Ti) and Si and M by Si
1-XM
XExpression; 0.1≤X when M is Mn≤0.7, when M is Ti in the fused solution that does not contain undissolved C of the alloy of 0.1≤X≤0.25; The crystal seed substrate of dipping silit; The cold silit that makes of mistake of the alloy molten liquid through the crystal seed substrate periphery is in hypersaturated state, on the crystal seed substrate, grows silicon carbide seed crystal thus.And, for the method for manufacture that the spy opens the single-crystal silicon carbide that the 2000-264790 communique put down in writing, put down in writing: owing to the carbon that adds as raw material causes the easier crystallization of silit.
The spy opens the method for manufacture that the 2006-143555 communique has been put down in writing a kind of single-crystal silicon carbide; Wherein, The crystal seed substrate of dipping silit in the fused solution of alloy; Make the alloy molten liquid of crystal seed substrate periphery be in the hypersaturated state of silit, growing silicon carbide crystal seed on the crystal seed substrate thus, said alloy contains Si, C and M (side of M:Fe or Co); And when the volumetric molar concentration that the volumetric molar concentration of M is made as [M], Si was made as [Si], the value of [M]/([M]+[Si]) during for Fe was 0.2～0.7 at M, be 0.05～0.25 at M during for Co., for the not identification of macroscopic defects of crystal growing surface.
The spy opens the method for manufacture that the 2007-7986 communique has been put down in writing a kind of single-crystal silicon carbide; Wherein, The single crystal substrate that growth of silicon carbide is used contacts with fused solution, and the cold silit that is fused to fused solution that makes of mistake of the fused solution through single crystal substrate periphery is in hypersaturated state, thus growing silicon carbide single crystal on single crystal substrate; Said fused solution is to contain Si, Ti, M (M:Co and/or Mn) and C, and the atomic ratio of Si, Ti and M is by Si
xTi
yM
ZThe fused solution of 0.17≤y/x≤0.33 and 0.90≤(y+z)/x≤1.80 is satisfied in expression, or contains Si, Ti, M (M:Al) and C, and the atomic ratio of Si, Ti and M is by Si
xTi
yM
ZThe fused solution of 0.17≤y/x≤0.33 and 0.33≤(y+z)/x≤0.60 is satisfied in expression., for the not identification of macroscopic defects of crystal growing surface.
Summary of the invention
As previously discussed, in the block method for monocrystal growth of the silit of the employing solution method that known document is put down in writing,, be difficult to realize the raising of the form of crystal growth laminar surface for the not identification of macroscopic defects on growing crystal surface.
The result that present inventors discuss for the silicon carbide monocrystal growth method of this employing solution method finds; Through in the Si-Cr-C fused solution, adding the Cr more than a certain amount of; Can obtain the bigger speed of growth; But the surface of the silicon carbide monocrystal growth layer that employing Si-Cr-C fused solution obtains is unstable; The change of small growth conditions all causes detrimentally affect to the surface of grown layer, and promptly the form (form) on growing crystal surface is insufficient, and then sometimes the quality of the growing crystal that obtains is impacted.
The silicon carbide monocrystal growth method of raising that the purpose of this invention is to provide the form of the crystal growth laminar surface of realizing solution method.
The present invention relates to a kind of growth method of single-crystal silicon carbide; Thereby single-crystal silicon carbide is contacted with the heated fused solution that has melted Si in plumbago crucible grows single-crystal silicon carbide on single crystal substrate; This growth method is characterised in that; Make above-mentioned single-crystal silicon carbide separate out and grow from the Si-Cr-X-C fused solution that in above-mentioned fused solution, has added Cr and X (X be among Ni and the Co at least a) element; Ratio as Cr in total composition and X element is a following ranges, and promptly Cr is that 30～70 atom %, X are 1～25 atom %.
According to the present invention, can realize the raising of the form of crystal growth laminar surface, and compare with the solution method that known document is put down in writing, can make silicon carbide monocrystal growth with the equal above speed of growth.
Description of drawings
Fig. 1 representes to be used for 1 embodiment of manufacturing installation of the method for embodiment of the present invention.
Fig. 2 is illustrated in the device that carries out the growth experiment of single-crystal silicon carbide in each example.
Fig. 3 A is illustrated in the Si that obtains in the comparative example 1: Cr ratio of components (atom %) is the photo of form of crystal growth laminar surface of 50: 50 o'clock carborundum crystals.
Fig. 3 B is illustrated in the Si that obtains in the comparative example 1: Cr ratio of components (atom %) is the photo of form of crystal growth laminar surface of 60: 40 o'clock carborundum crystals.
Fig. 4 is illustrated in the photo of form of the crystal growth laminar surface of the carborundum crystals that obtains among the embodiment 1.
Embodiment
For the present invention, the Fig. 1 of 1 embodiment of manufacturing installation that is used for the method for embodiment of the present invention with reference to expression explains.
In Fig. 1, silicon carbide monocrystal growth is through using the plumbago crucible that surrounded by thermal insulation material 65 to implement as reaction vessel.For the fused solution 2 that heats by radio-frequency coil 1 as heating unit; On the termination of graphite rod 3 (being also referred to as graphite shaft), engage as 1 example of silicon carbide seed crystal support member, the fixing single crystal substrate 4 that constitutes by single-crystal silicon carbide; Thereby it impregnated in make single crystal substrate 4 growths in the fused solution 2, can realize silicon carbide monocrystal growth thus.
In the silicon carbide monocrystal growth method of employing solution method in the present invention; It is necessary making carborundum crystals separate out growth from the Si-Cr-X-C fused solution; Said Si-Cr-X-C fused solution is the fused solution that has added Cr and X (X be among Ni and the Co at least a) element with Si and C; Ratio as Cr in total composition and X is a following ranges, and promptly Cr is 30～70 atom %, and X is 1～25 atom % (more than the 1 atom % and less than 25 atom %), is preferably 3～7 atom %.
Do not use simultaneously Cr and X, for example specially open Mo-Si-C3 element, Cr-Si-C3 element, the Co-Si-C3 element of expressing as concrete example in the 2000-264790 communique, though can expect the improvement of the speed of growth, the crystalline quality of separating out is insufficient.
In addition, in the Si-Cr-X-C fused solution, if Cr is less than 30 atom %; Then the speed of growth of single-crystal silicon carbide significantly diminishes, if more than 70 atom %, then around single-crystal silicon carbide with polycrystal; Be difficult to stably have only the growth of monocrystalline, therefore inappropriate.In addition, in the Si-Cr-X-C fused solution, if X is less than 1 atom %; Then can not improve the form on the surface of single-crystal silicon carbide, if more than 25 atom %, part or all polycrystallization of the carborundum crystals that then obtains; Be difficult to come stable growth, instead undesirable as monocrystalline.
In the present invention through using the Si-Cr-X-C fused solution of above-mentioned composition; The speed of growth of single-crystal silicon carbide increases; And the form of plane of crystal improves, and can think because improve owing to Cr makes the dissolving power of the C (carbon) of the graphite (being crucible among Fig. 1) that contacts from fused solution as its reason; This C becomes the raw material of carborundum crystals as a result, and X reduces the energy of solid-liquid interface or the surface energy of fused solution (solution).
As the Si-Cr-X-C fused solution of the above-mentioned composition of modulation in the method for the present invention to obtain the method for single-crystal silicon carbide; Have no particular limits; For example, at first Si, Cr and X are joined in the plumbago crucible as reaction vessel as raw material, make the raw material fusing; Be heated to the high temperature of solidus temperature, form fused solution than the alloy that generates.In addition, at least a portion of the C in the above-mentioned Si-Cr-X-C fused solution is dissolved into the fused solution from plumbago crucible, and is preferred especially through supplying with whole C from the dissolving of plumbago crucible.In addition, thus also can carbide, carbon be added the C of a part as raw material.And then, can also enumerate the method that is blown into the C that supplies with a part in the fused solution through carbonaceous gas with methane etc.
Continue the heating of fused solution; Raw material that crucible, Si, Cr and X constituted and C fully melt; Be the silit saturation concentration of solvent and reach constant if the carbon concentration in the fused solution that generates approaches with the fused solution; The crystal seed substrate that growth of silicon carbide is used contacts with fused solution; For example be employed in the temperature gradient method of establishing the thermograde about 5～50 ℃/cm in the fused solution or operate heating unit fused solution refrigerative method of cooling; The fused solution of crystal seed substrate periphery is crossed be as cold as below 2100 ℃, the temperature about 1600～1800 ℃ particularly, make the silit that is dissolved in fused solution be in hypersaturated state, single-crystal silicon carbide is grown on single crystal substrate.
As single crystal substrate, the preferred use and single crystal substrate as the identical crystalline form of the silit of target.For example can use the single-crystal silicon carbide that adopts subliming method to make.
In the method for the invention, but itself known manufacturing process, the for example shape of plumbago crucible, heating means, heat-up time, atmosphere, heat-up rate and the speed of cooling in the applying soln method.
For example; Can enumerate high-frequency induction heating as heating means; As heat-up time (reaching the general time of SiC saturation concentration from being encased in of raw material) though also depend on the size of crucible; But be (for example about 3～7 hours) about several hours～10 hours,, can enumerate the rare gas for example rare gas element, the atmosphere that their part is formed with the displacement of N2, methane gas of He, Ne, Ar etc. as atmosphere.
According to the method for the invention; Compare with the silicon carbide monocrystal growth method of the use solution method of known 3 compositions system (for example, Si-Cr-C fused solution system) or 4 compositions system (for example Si-Ti-Al-C fused solution system, Si-Ti-Mn-C fused solution system, Si-Ti-Co-C fused solution system) in the past; Can not contain multicrystal single-crystal silicon carbide in fact with equal above speed of growth manufacturing, preferably produce n type single-crystal silicon carbide.
And, according to the method for the invention, can make the single-crystal silicon carbide of the raising of the form that has realized the crystal growth laminar surface.
Much less method of the present invention can be applicable to the growth method of bulk-shaped monocrystal, also can be applicable to form technology at the liquid phase epitaxial layer of silicon carbide substrate surface.
Embodiment
Embodiments of the invention below are shown.
In each following example, use the growth experiment that plumbago crucible shown in Figure 2 has been carried out single-crystal silicon carbide as the device of reaction vessel.In addition, graphite rod 3 is built-in W-Re thermopair 7, and, in plumbago crucible 5, be provided with radiation thermometer 8.
In plumbago crucible 5, add Si and then add Cr and X simultaneously; Continue about 2～3 hours heating; Maintain design temperature (1800～2100 ℃); From plumbago crucible 5 dissolving C, in the fused solution 2 that has reached the silit saturation concentration, be immersed in the monocrystalline silicon carbide substrate of installing on the termination of graphite rod 34 then.Remain on design temperature; Operate radio-frequency coil 1 then as heating unit; For the fused solution temperature, the front of the crystal (not shown) in single crystal substrate 4 and growth is provided with the thermograde of 0.8～3.0 ℃/mm, and single-crystal silicon carbide is grown on single crystal substrate 4.After having passed through growth time, fully mention growing crystal, with plumbago crucible 5 slow cool to room temperature, the single-crystal silicon carbide that obtains growing from fused solution 2.
For the carborundum crystals that in each embodiment, obtains, the form of crystal growth laminar surface is observed through visual and microscope.In addition, for the carborundum crystals that in each embodiment, obtains, utilize X ray (XRD) to confirm monocrystalline or polycrystal.
Comparative example 1
Add in the plumbago crucible respectively the do for oneself raw material of 45 atom % and 45 atom % of the proportion of composing of Si and Cr to heat fused.Remain on certain temperature, carried out crystal growth in the solution thereby single crystal substrate impregnated in.Confirmed that the carborundum crystals that obtains is a monocrystalline.
The temperature measuring of solution etc., as shown in Figure 2, use radiation thermometer and thermopair, but radiation thermometer is arranged at the viewing window of the solution face top of direct viewing solution face, can measure the temperature that makes the front and back that radiation thermometer contacts with solution.In addition, thermopair is set, measures with solution and rigidly connect temperature after touch in the inboard (apart from the position of single crystal substrate 2mm) of the graphite rod that has engaged single crystal substrate.
The speed of growth of single-crystal silicon carbide is 210 μ m/h.
In addition, the form of crystal growth laminar surface is shown in Fig. 3 A and Fig. 3 B.Fig. 3 A representes Si: the Cr ratio of components is the situation of 50: 50 atom %, and Fig. 3 B representes Si: the Cr ratio of components is the situation of 60: 40 atom %.Can know that by Fig. 3 A and Fig. 3 B when utilizing the Si-Cr-C fused solution, for the form (state) of the growth surface of single-crystal silicon carbide, a fairly large number of step is apparent in its surface, for form bad.
Add in the plumbago crucible 5 respectively the do for oneself raw material of 50 atom %, 45 atom % and 5 atom % of the proportion of composing of Si, Cr and Ni to heat fused.Remain on certain temperature, single crystal substrate impregnated in the solution, carried out crystal growth.Confirmed that the carborundum crystals that obtains is a monocrystalline.
Likewise carried out temperature measuring, the morphologic observation of solution etc. with comparative example 1, the speed of growth of single-crystal silicon carbide is measured.
The speed of growth of SiC monocrystalline is 240 μ m/h.
In addition, the form of crystal growth laminar surface is shown in Fig. 4.Confirm that by Fig. 4 when utilizing the Si-Cr-Ni-C fused solution, the form of the growth surface of single-crystal silicon carbide significantly improves.
Comparative example 2
The ratio of Al is changed in the scope of 0～10 atom %; The raw material of Si, Ti and Al is packed in the plumbago crucible 5, and heat fused remains on certain temperature (about 1810 ℃); Crystal seed impregnated in the solution, likewise carried out crystal growth with embodiment 1 in addition.
In Si-Ti-Al-C fused solution system, even Zong change the ratio of the Al in forming, the speed of growth is up to below the 140 μ m/h.
Add in the plumbago crucible 5 respectively the do for oneself raw material of 50 atom %, 45 atom % and 5 atom % of the proportion of composing of Si, Cr and Co to heat fused.Remain on certain temperature, single crystal substrate impregnated in the solution, carried out crystal growth.Confirmed that the carborundum crystals that obtains is a monocrystalline.
Likewise carried out temperature measuring, the morphologic observation of solution etc. with comparative example 1, the speed of growth of single-crystal silicon carbide is measured.
The speed of growth of single-crystal silicon carbide is 225 μ m/h.
In addition, the form of crystal growth laminar surface is identical with Fig. 4.By this results verification when utilizing the Si-Cr-Co-C fused solution, the form of the growth surface of single-crystal silicon carbide significantly improves.
Comparative example 3
Do not add Ni, the ratio of Cr is changed in the scope of 3～95 atom %, in the raw material adding plumbago crucible 5 with Si and Cr; Heat fused; Remain on certain temperature (about 1980 ℃), crystal seed impregnated in the solution, likewise carried out crystal growth with embodiment 1 in addition.
The form and the comparative example 1 of the crystal growth laminar surface of the carborundum crystals that obtains are likewise bad, and in addition, if the ratio of the Cr in Si and the Cr total amount is more than 70 atom %, the part of the carborundum crystals that then obtains is all polycrystallizations perhaps.
Utilize possibility on the industry
Silicon carbide monocrystal growth method of the present invention has the high temperature of realization, high frequency, proof voltage and environment resistant possibility, can obtain having the single-crystal silicon carbide as the possibility of follow-on semiconductor material.
In addition, silicon carbide monocrystal growth method of the present invention can realize the raising of the form of growth of silicon carbide plane of crystal.
And silicon carbide monocrystal growth method of the present invention is compared with known solution method in the past, can make silicon carbide monocrystal growth with equal above crystalline growth velocity.
Among the present invention the expression numerical range " more than " and " following " include given figure.
Claims (7)
1. the growth method of a single-crystal silicon carbide; Thereby single-crystal silicon carbide is contacted with the heated fused solution that has melted Si in plumbago crucible grows single-crystal silicon carbide on single crystal substrate; This growth method is characterised in that; Make said single-crystal silicon carbide separate out and grow from the Si-Cr-X-C fused solution that in said fused solution, has added Cr and X element; Wherein X is at least a among Ni and the Co, is that following ranges: Cr is that 30～70 atom %, X are 1～25 atom % as the ratio of Cr in total composition and X element.
2. growth method according to claim 1 wherein, is the scope interpolation X of 3～7 atom % with ratio.
3. growth method according to claim 1 wherein, is added Si, Cr and X in the plumbago crucible to as raw material, makes the raw material fusing, is heated to the high temperature of solidus temperature than the alloy that generates, and modulates said fused solution.
4. growth method according to claim 1, wherein, at least a portion of the C in the said fused solution is melted to the fused solution from said plumbago crucible.
5. growth method according to claim 1 wherein, is supplied with whole C by plumbago crucible.
6. growth method according to claim 1, wherein, said single crystal substrate have with as the identical crystalline form of the silit of target.
7. growth method according to claim 1 wherein, is used to the growth of bulk-shaped monocrystal.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007306367A JP4277926B1 (en) | 2007-11-27 | 2007-11-27 | Growth method of silicon carbide single crystal |
| JP306367/2007 | 2007-11-27 | ||
| PCT/JP2008/071277 WO2009069564A1 (en) | 2007-11-27 | 2008-11-18 | Process for growing single-crystal silicon carbide |
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| CN101796227A CN101796227A (en) | 2010-08-04 |
| CN101796227B true CN101796227B (en) | 2012-09-26 |
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| CN2008800253811A Expired - Fee Related CN101796227B (en) | 2007-11-27 | 2008-11-18 | Process for growing single-crystal silicon carbide |
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| US (1) | US8685163B2 (en) |
| JP (1) | JP4277926B1 (en) |
| KR (1) | KR101085690B1 (en) |
| CN (1) | CN101796227B (en) |
| DE (1) | DE112008003497B4 (en) |
| WO (1) | WO2009069564A1 (en) |
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| DE112009005084B4 (en) | 2009-07-21 | 2016-05-12 | Toyota Jidosha Kabushiki Kaisha | IMPF CRYSTAL AXLE FOR ONE-CRYSTAL SOLUTION GROWTH |
| JP5428706B2 (en) * | 2009-09-25 | 2014-02-26 | トヨタ自動車株式会社 | Method for producing SiC single crystal |
| US10167573B2 (en) * | 2010-11-26 | 2019-01-01 | Shin-Etsu Chemical Co., Ltd. | Method of producing SiC single crystal |
| JP5287840B2 (en) * | 2010-12-16 | 2013-09-11 | 株式会社デンソー | Silicon carbide single crystal manufacturing equipment |
| JP5568054B2 (en) | 2011-05-16 | 2014-08-06 | トヨタ自動車株式会社 | Manufacturing method of semiconductor device |
| DE112013002107B4 (en) * | 2012-04-20 | 2019-04-04 | Toyota Jidosha Kabushiki Kaisha | SiC single crystal production method |
| JP5828810B2 (en) * | 2012-07-18 | 2015-12-09 | 新日鐵住金株式会社 | SiC single crystal manufacturing apparatus used in solution growth method, crucible used in the manufacturing apparatus, and SiC single crystal manufacturing method using the manufacturing apparatus |
| EP2940196B1 (en) * | 2012-12-28 | 2017-03-15 | Toyota Jidosha Kabushiki Kaisha | Method for producing n-type sic single crystal |
| JP5761264B2 (en) * | 2013-07-24 | 2015-08-12 | トヨタ自動車株式会社 | Method for manufacturing SiC substrate |
| JP5854013B2 (en) | 2013-09-13 | 2016-02-09 | トヨタ自動車株式会社 | Method for producing SiC single crystal |
| CN106012021B (en) * | 2016-06-30 | 2019-04-12 | 山东天岳先进材料科技有限公司 | A kind of seed shaft and method of liquid growth silicon carbide |
| CN106521629B (en) * | 2016-09-19 | 2018-12-28 | 山东天岳晶体材料有限公司 | A kind of method obtaining liquid silicon and the crucible for realizing this method |
| JP2019151530A (en) * | 2018-03-05 | 2019-09-12 | 国立大学法人信州大学 | MANUFACTURING METHOD OF SiC SINGLE CRYSTAL |
| CN114232097A (en) * | 2021-12-31 | 2022-03-25 | 广州半导体材料研究所 | Method for preparing silicon carbide single crystal |
| CN116926670B (en) * | 2023-07-12 | 2024-04-16 | 通威微电子有限公司 | Method for preparing silicon carbide by liquid phase method and prepared silicon carbide |
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| CN1922346A (en) * | 2004-12-28 | 2007-02-28 | 松下电器产业株式会社 | Method for producing silicon carbide (SiC) single crystal and silicon carbide (SiC) single crystal obtained by such method |
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| US7014336B1 (en) * | 1999-11-18 | 2006-03-21 | Color Kinetics Incorporated | Systems and methods for generating and modulating illumination conditions |
| JP2000264790A (en) | 1999-03-17 | 2000-09-26 | Hitachi Ltd | Production of silicon carbide single crystal |
| US6837605B2 (en) * | 2001-11-28 | 2005-01-04 | Osram Opto Semiconductors Gmbh | Led illumination system |
| JP4100228B2 (en) | 2002-04-15 | 2008-06-11 | 住友金属工業株式会社 | Silicon carbide single crystal and manufacturing method thereof |
| JP4118742B2 (en) * | 2002-07-17 | 2008-07-16 | シャープ株式会社 | Light emitting diode lamp and light emitting diode display device |
| TWI282022B (en) * | 2003-03-31 | 2007-06-01 | Sharp Kk | Surface lighting device and liquid crystal display device using the same |
| US7334918B2 (en) * | 2003-05-07 | 2008-02-26 | Bayco Products, Ltd. | LED lighting array for a portable task light |
| US20040228127A1 (en) * | 2003-05-16 | 2004-11-18 | Squicciarini John B. | LED clusters and related methods |
| CN1864027B (en) * | 2003-10-06 | 2010-08-25 | 照明管理解决方案有限公司 | Light source using light emitting diodes and an improved method of collecting the energy radiating from them |
| KR100638611B1 (en) * | 2004-08-12 | 2006-10-26 | 삼성전기주식회사 | Light emitting diode having multiple lenses |
| JP4934958B2 (en) | 2004-11-24 | 2012-05-23 | 住友金属工業株式会社 | Method for producing silicon carbide single crystal |
| JP2006321681A (en) | 2005-05-19 | 2006-11-30 | Toyota Motor Corp | Method for producing silicon carbide single crystal |
| JP4419937B2 (en) | 2005-09-16 | 2010-02-24 | 住友金属工業株式会社 | Method for producing silicon carbide single crystal |
| JP2007261844A (en) * | 2006-03-28 | 2007-10-11 | Sumitomo Metal Ind Ltd | Manufacturing method of silicon carbide single crystal |
| CN102003636A (en) * | 2009-09-03 | 2011-04-06 | 富准精密工业(深圳)有限公司 | Light-emitting diode (LED) module |
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- 2008-11-18 CN CN2008800253811A patent/CN101796227B/en not_active Expired - Fee Related
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- 2008-11-18 KR KR1020097023496A patent/KR101085690B1/en active IP Right Grant
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| CN1922346A (en) * | 2004-12-28 | 2007-02-28 | 松下电器产业株式会社 | Method for producing silicon carbide (SiC) single crystal and silicon carbide (SiC) single crystal obtained by such method |
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| JP特开2004-2173A 2004.01.08 |
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Also Published As
| Publication number | Publication date |
|---|---|
| JP4277926B1 (en) | 2009-06-10 |
| US20100236472A1 (en) | 2010-09-23 |
| JP2009126770A (en) | 2009-06-11 |
| KR20090129514A (en) | 2009-12-16 |
| KR101085690B1 (en) | 2011-11-22 |
| DE112008003497B4 (en) | 2015-06-25 |
| WO2009069564A1 (en) | 2009-06-04 |
| US8685163B2 (en) | 2014-04-01 |
| DE112008003497T5 (en) | 2010-10-28 |
| CN101796227A (en) | 2010-08-04 |
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